Physico-Chemical nanomaterials science 

Composites of Co and Ni nanoparticles for hydrogenation of substituted quinolines
Kolotilov S.V.1, Asaula V.M.1,  Buryanov V. V.2, Ivanytsya M. O.1,2, Volochnyuk D. M.2,3, Ryabukhin S. V.2
1 L.V.Pisarzhevskii Institute of Physical Chemistry of the National Academy of Sciences of Ukraine. Prospect Nauki, 31, Kyiv-03028, Ukraine. 
E-mail: nvgrab@gmail.com
2 Enamine Ltd, Kyiv, Ukraine, A. Matrosova str. 23, Kyiv-01103
3 Institute of Organic Chemistry of the NAS of Ukraine, Murmanska str., 5, Kyiv-02000, Ukraine 

Reactions of organic compounds catalytic hydrogenation are widely used for synthesis of active pharmaceutical ingredients, compounds for agriculture, etc. In the majority of cases such processes are carried out at presence of catalysts based on platinum group (PG) metals. Development of PG-metal-free composites, possessing high catalytic activity in the processes of hydrogenation, is actual task, because use of such systems allows to decrease consumption of precious metals as well as to reduce pollution of the products by toxic PG ions (catalyst component). 
In this work the composites, containing on Co or Ni nanoparticles and/or their oxides, N-doped carboneous particles on porous carriers (SiO2, Al2O3, ZrO2, carbon) were studied. The composites were prepared by pyrolysis of the coordination compounds with N-containing organic ligands, deposited on the corresponding carrier. It was shown by TEM and Raman spectroscopy that the composites contained carboneous particles of ca. 10-50 nm size, which had more than 8 carbon monolayers. Co and Ni were in the form of metals or metal oxides, as shown by powder X-ray diffraction.
The obtained nanocomposites were catalytically active in hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline by gaseous H2 at 30-50 atm pressure and temperature 50-150 ºC. The yield of tetrahydroquinoline varied from 40 to almost 100 % depending on the method of composite preparation and the reaction conditions. Hydrogenation selectivity was studied for a row of quinolines, bearing substituents (Br, Cl, CH3, OCH3 etc.) in different positions. The method for quick evaluation of catalytic activity of the composites in hydrogenation reactions was proposed.